CN1504490A - Polyisocyanates solution , adhesive and paint using the same - Google Patents
Polyisocyanates solution , adhesive and paint using the same Download PDFInfo
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- CN1504490A CN1504490A CNA200310119752A CN200310119752A CN1504490A CN 1504490 A CN1504490 A CN 1504490A CN A200310119752 A CNA200310119752 A CN A200310119752A CN 200310119752 A CN200310119752 A CN 200310119752A CN 1504490 A CN1504490 A CN 1504490A
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Abstract
Provided is a polyisocyanate solution having excellent solvent solubility, compatibility with other resins and curability, and exhibiting suitable hardness, adhesivity, close contact, etc., when used as an adhesive or a coating material. This polyisocyanate solution is constituted by including an isocyanate group-terminated urethane prepolymer (A) obtained by reacting an organic polyisocyanate (A1) with a polyol (A2) comprising 20-40 mol% diol (A2-1) having an alcoholic hydroxy group and 80-60 mol% triol (A2-2) having an alcoholic hydroxy group and an organic solvent (B), wherein part of the triol (A2-2) is glycerol and 15-35 mol% of the polyol (A2) is glycerol.
Description
Technical field
The present invention relates to a kind of polyisocyanate solution and use the caking agent and the coating of this polyisocyanate solution.
Background technology
Polyisocyanate solution is owing to contain the isocyanate group of a plurality of hyperergys, thereby has under the normal temperature also easily and contain the character of the compound reaction of reactive hydrogen.The urethanes that is obtained by this polyisocyanate solution is owing to have performances such as good cementability, wear resistance, weathering resistance, so be widely used in fields such as caking agent and coating.
Make such polyisocyantates composition and the compound combination that contains reactive hydrogen, when thus serving as polyurethane adhesive or polyurethane coating, the molecular weight of polyisocyantates composition, functional group's number have bigger influence to the reactivity of the polyurethane system in polyurethane adhesive or the polyurethane coating, duration of service, consistency etc., greatly influence the performance and the operability of this system.
Therefore, when making polyisocyantates composition, need preparation to be fit to the composition with suitable molecular weight and functional group's number of purposes.As its standard, under situation, the consistency of the solvability of solvent and active hydrogen compounds, hardening etc. are used as index as caking agent or coating.In order suitably to regulate its performance, the adjustment that the composition of selection of catalysts, various raw materials, its adding when add reaction conditionss such as method, temperature of reaction, reaction times is very important.Isocyanic ester is because it has the low tendency of consistency that contains the compound of reactive hydrogen with glycol, triol, polyether glycol etc. in essence, therefore utilize between the isocyanic ester reaction or and the reaction of active hydrogen compounds when obtaining polyisocyantates composition, for the solvability that improves the relative solvent of polyisocyanate solution etc. has been carried out various tests.
For example the spy opens and discloses a kind of polyisocyantates composition in the 2002-60459 communique, by introducing the allophanic acid ester bond, improves the solvability with respect to non-polar organic solvent, odorless solvent.
A kind of modified polyisocyanate wax is disclosed in the Te Kaiping 6-256663 communique, alcohol mixture and isocyanate reaction that the aliphatic polyol that cooperates 1～50 mole of % in the straight chain aliphatic primary alcohol of carbon number 10～30 is formed, the modified polyisocyanate wax of formation has the good solvability to organic solvent.
Disclose a kind of method in the Te Kaiping 9-40738 communique, when utilizing the reaction of isocyanic ester and polynary ester polyol to obtain urethane, used the 2-methyl isophthalic acid, ammediol improves the solvability of relative common solvent thus as its polyester polyol composition.
A kind of method is disclosed in the Te Kaiping 5-155971 communique, polyhydroxy reactant as polyester polyol, use molecular weight 300～3, addition polymerization epoxide on 000 polytetramethylene ether diol, compound or the dihydric phenol with two hydroxy phenyls, the molecular weight 1 that obtains, polyether polyols below 000, the solvability of raising solvent.
Although the solvent solubility that improves polyisocyanate solution has been carried out all trials, but the reaction of active hydrogen compounds such as utilization and glycol or triol obtains the solvent solubility of isocyanate group terminal amino group manthanoate prepolymer still to be difficult to argue think, needs further to improve.
In order to bring into play in caking agent or the paint field necessary performances such as hardness, cementability and stopping property, need good and the consistency of other resin, indurative polyisocyanate solution.But when the method that adopts general reduction functional group number during as the method that improves with the consistency of other resin of active hydrogen compounds, the problem of appearance is along with the necessary hardening of the reduction of functional group's number also reduces.Although can improve hardening by adding catalyzer, wish to find a kind of method, do not use catalyzer, improve the composition of polyisocyanates, raising consistency and hardening two characteristics.
Isocyanate group in the polyisocyantates composition has very high reactivity, thereby not only aspect the molecular weight of control during above-mentioned reaction, and aspect stability in storage, also usually have problems, up to now, people are carrying out various researchs for improving this stability in storage always.
For example the spy opens to disclose in the flat 5-247174 communique and makes Polyhydroxypolyether, and excessive tolylene diisocyanate reaction, can obtain polyisocyanates.
Te Kaiping 8-283367 communique discloses the method for using methyl tosylate, ethyl p-toluenesulfonate class stopper; Disclose a kind of method in the Te Kaiping 9-194557 communique,, added water-disintegrable transistion metal compound as water-removal agent containing trialkylsilkl thioether group compound and having in the composition that the compound of isocyanate group forms.
The spy opens clear 59-98050 communique and discloses a kind of method of improving stability, in order to improve the painted stability that organic multiple isocyanate causes air, light, heat etc., in organic multiple isocyanate, add organic phosphites and 2 such as didecyl pentaerythritol diphosphate, 6-di-tert-butyl-4-methy phenol and 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole and organic multiple isocyanate are also used.
Disclose the method for improving stability in the Te Kaiping 5-117220 communique, when obtaining the chlorinated isocyanurates modified polyisocyanate, before (film) distillation, added specific organic system strong acid silylanizing ester.
Although carried out all trials aspect the polyisocyanate solution stability improving, its characteristic is still dissatisfied, needs to improve further.And require to obtain having good hardening, solvent solubility and stability in storage, and has the polyisocyanate solution of necessary hardness, cementability and stopping property thereof etc. of good caking agent or paint field.
Summary of the invention
The objective of the invention is to, on the basis of the described fact, provide a kind of and have the excellent solvent solvability, have consistency and hardening other resin, and performance is in the polyisocyanate solution of the suitable hardness of occasions such as caking agent or coating, cementability and stopping property etc., and the coating and the caking agent that contain this solution.
Another object of the present invention is to, provide a kind of and not only have above-mentioned each characteristic, and have the polyisocyanate solution of good stability in storage.
The inventor has carried out research in depth to achieve these goals, the result shows, the polyisocyanate solution that contains the isocyanate group terminal amino group manthanoate prepolymer (A) of regulation and organic solvent (B) not only has the excellent solvent solvability, to the consistency and the hardening of other resin, and have good caking agent or necessary hardness, cementability and a stopping property of paint field, find in this polyisocyanate solution, to cooperate etheride can significantly improve the stability in storage of polyisocyanate solution simultaneously, until finishing the present invention.
Just, the invention provides
1. polyisocyanate solution, contain organic multiple isocyanate (A1) and by 20～40 moles of % of the glycol with alcoholic hydroxyl (A2-1) and have isocyanate group terminal amino group manthanoate prepolymer (A) and an organic solvent (B) that polyvalent alcohol (A2) reaction that 80～60 moles of % of triol (A2-2) of alcoholic hydroxyl form obtains
It is characterized in that the part of described triol (A2-2) is a glycerol, 15～35 moles of % of described polyvalent alcohol (A2) are described glycerol simultaneously.
2. as 1 described polyisocyanate solution, it is characterized in that described organic multiple isocyanate (A1) is a tolylene diisocyanate.
3. as 1 or 2 described polyisocyanate solution, it is characterized in that, contain etheride (C).
4. a caking agent is characterized in that, uses any one described polyisocyanate solution in 1～3.
5. a coating is characterized in that, uses any one described polyisocyanate solution in 1～3.
Embodiment
Below the present invention will be described in more detail.
The polyisocyanate solution that the present invention relates to, contain isocyanate group terminal amino group manthanoate prepolymer (A) and organic solvent (B) as mentioned above, wherein isocyanate group terminal amino group manthanoate prepolymer (A) is to be obtained by the reaction of organic multiple isocyanate (A1) and polyvalent alcohol (A2), and polyvalent alcohol (A2) is made of 20～40 moles of % of the glycol with alcoholic hydroxyl (A2-1) and 80～60 moles of % of triol (A2-2) with alcoholic hydroxyl; It is characterized in that triol (A2-2) part is a glycerol, 15～35 moles of % of polyvalent alcohol (A2) are glycerol simultaneously.
(A1) can use as organic isocyanate: the compound that has 2 above isocyanate group in 1 molecule, for example toluene supports vulcabond (hereinafter to be referred as TDI), diphenylmethanediisocyanate (hereinafter to be referred as MDI), MDI and MDI are the mixture (hereinafter to be referred as polycondensation MDI) of multinuclear condenses, xylylene diisocyanate, the diphenyl ether vulcabond, the dimethyl diphenylmethane vulcabond, phenylene vulcabond, naphthalene diisocyanate, aromatic diisocyanates such as tetramethylxylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter to be referred as HDI), the 3-methyl isophthalic acid, 5-pentane vulcabond, aliphatic diisocyanates such as rosin vulcabond, isophorone diisocyanate, hydrogenation toluene support vulcabond, the hydrogenation Xylene Diisocyanate, the hydrogenation diphenylmethanediisocyanate, alicyclic diisocyanates such as hydrogenation tetramethyl-benzene diformazan phenylene diisocyanate etc.
In addition, also can use the biuret after a part of modification of isocyanate group, allophanate, chlorinated isocyanurates (trimer), urinate the material of modifications such as diketone (ウ レ ト ジ オ Application) (dipolymer), carbodiimide, urine imines modifier, oxazolidones such as (ウ レ ト Application イ ミ Application) (オ キ サ ゾ リ De Application), acid amides, imines.
Above-mentioned organic isocyanate class (containing its modifier) can be used separately also and can mix use.
In above-mentioned organic isocyanate, consider that normal temperature is that liquid state is handled easily, its modifier has characteristics such as good rerum natura is simultaneously economic and practical, preferably uses TDI, preferred especially 2,4-TDI is 100～50 quality %, 2, and 6-TDI is the TDI that 0～50 quality % forms.
Polyvalent alcohol (A2) is a kind of by the glycol with alcoholic hydroxyl (A2-1) with have the material that the triol (A2-2) of alcoholic hydroxyl is formed.
In this case, the constituent ratio of dibasic alcohol (A2-1) and trivalent alcohol (A2-2) is that dibasic alcohol (A2-1) is 20～40 moles of % in the polyvalent alcohol (A2), and preferred 25～35 moles of %, trivalent alcohol (A2-2) are 80～60 moles of %, preferred 75～65 moles of %.Dibasic alcohol (A2-1) is than 20 moles of % (just trivalent alcohol (A2-2) situation about Duoing than 80 moles of %) after a little while, when the polyisocyanate solution that obtains with the present invention is used stiffening agent as caking agent or coating, rerum naturas such as hardening improves, while hardness and drying property thereof improve; But, the solvability in organic solvent, other the consistency of resin is reduced because viscosity improves.Dibasic alcohol (A2-1) is than 40 moles of % (just trivalent alcohol (A2-2) situation about lacking than 60 moles of %) for a long time, the polyisocyanate solution that the present invention obtains is used under the situation of stiffening agent as caking agent or coating, though the solvability in the organic solvent and the consistency of other resin improve, rerum naturas such as but hardening reduces, while hardness or drying property reduce.
As whole (number average) molecular weight preferred 32～10,000, preferred especially 100～5,000 of polyvalent alcohol (A2).The viscosity of the polyisocyanate solution that consideration the present invention obtains and isocyanate content etc., (number average) molecular weight less than 500 of polyvalent alcohol (A2) integral body is optimum.
Be not particularly limited as above-mentioned glycol (A2-1) with alcoholic hydroxyl, for example have: ethylene glycol, Diethylene Glycol, triethylene glycol, 1, the 2-propylene glycol, 1, ammediol, dipropylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, neopentyl glycol, the 3-methyl isophthalic acid, the 5-pentanediol, hexanaphthene-1, the 4-glycol, hexanaphthene-1, the 4-dimethanol, monoethanolamine, N methyldiethanol amine, the N-phenyldiethanol-amine, low molecule amino alcohols such as N-phenyl dipropanolamine are glycols, low-molecular-weight diol classes such as hydrogenation dihydroxyphenyl propane, make low molecule cyclic ether such as above-mentioned low-molecular-weight diol class open loop addition alkylidene group epoxide obtain containing amino polyether glycol, make above-mentioned low-molecular-weight diol class and Succinic Acid, hexanodioic acid, nonane diacid, the polyester glycol class that dicarboxylic acid generation dehydration condensations such as phthalic acid obtain, the lactone that cyclic ester monomer such as above-mentioned low-molecular-weight diol class ring-opening polymerization ε-Ji Neixianan is obtained is a polyester glycol, makes above-mentioned low-molecular-weight diol class and has the polycarbonate diol class that the low molecular carbon ester compound reaction of 1 carbonate group obtains, the polyolefin polyhydric alcohol that has 2 alcoholic hydroxyl in 1 molecule, acrylic acid series multiple alcohol, polyhutadiene is a polyvalent alcohol, phenol such as Novolac resol and Rexol resol are polyvalent alcohol, silicon is polyvalent alcohol, fluorine is a polyvalent alcohol, in polyvalent alcohol, make vinyl monomers such as vinyl cyanide and vinylbenzene disperse radical polymerization to obtain polymer polyatomic alcohol etc.These can use a kind separately, also can mix use more than 2 kinds.
Trivalent alcohol (A2-2) with alcoholic hydroxyl is not particularly limited, for example have: glycerol, TriMethylolPropane(TMP), 2,3, it is polyester trivalent alcohol etc. that the cyclic ester monomers such as polyether-tribasic alcohol, above-mentioned low molecule ternary alcohols and ε-Ji Neixianan that it is the ternary alcohols that aliphatics such as 5-hexanetriol are hanged down low molecule amino alcohols such as molecule ternary alcohols, trolamine, tripropanol amine, low molecule cyclic ether openings such as these and alkylidene group epoxide are obtained carry out the lactone that ring-opening polymerization obtains, and these can use to mix more than a kind or 2 kinds and use.
Part in the trivalent alcohol (A2-2) is a glycerol, and is 15～35 moles of % of polyvalent alcohol (A2), preferred 17～33 moles of %, more preferably 18～32 moles of %.
The amount that contains glycerol in the polyvalent alcohol (A2) is worried reductions such as hardening, hardness, drying property during less than 15 moles of %.When the amount that contains glycerol in the polyvalent alcohol (A2) during more than 35 moles of %, worry that the viscosity of carbamate prepolymer uprises, also worry that the solvability in the organic solvent and the consistency of other resin also reduce simultaneously.
Described organic solvent (B) is so long as commonly used just passable with respect to isocyanate group inert solvent on the polyurethane industrial, be not particularly limited, for example toluene, aromatic series series solvents such as dimethylbenzene, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ketone series solvents such as pimelinketone, vinyl acetic monomer, N-BUTYL ACETATE, ester series solvents such as acetic acid isobutyl-, ethylene glycol monoethyl ether acetate, methyl proxitol acetate, 3-methyl-3-methoxyl group butylacetic acid ester, ethyl-glycol ether-ether series solvents such as 3-ethoxy-c acid esters, tetrahydrofuran (THF), ether series solvents such as dioxane etc.These solvents can use a kind, also can mix use more than 2 kinds.
The usage quantity of above-mentioned organic solvent (B) is not particularly limited, relative preferred 10～90 quality % of polyisocyanate solution, preferred especially 20～80 quality %.
In this case, preferred 10～90 quality % of the solid component content in the above-mentioned polyisocyanate solution, more preferably 20～80 quality %.And preferred 1～30 quality % under the isocyanate content solution state, preferred especially 2-25 quality %.
By above-mentioned (A), (B) preferably cooperate etheride (C) in the polyisocyanate solution that each composition constitutes.By in above-mentioned polyisocyanate solution, cooperating such etheride (C), can prevent in polyisocyanate solution between the shelf lives that active hydrogen compoundss such as isocyanate prepolymer composition in the solution and moisture react and the formation high molecular.The polyisocyanate solution stability in storage can improve further.
Spendable etheride (C) is the halogenide of aliphatics or aromatic carboxylic acid among the present invention.In this case, as aliphatics or aromatic carboxylic acid, be not particularly limited, for example have: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sad, capric acid, laurostearic acid, TETRADECONIC ACID, hexadecanoic acid, stearic acid, lactic acid, levulinic acid, vinylformic acid, methacrylic acid, valeric acid, propanedioic acid, toxilic acid, hexanodioic acid, nonane diacid, citric acid, pentanedioic acid, succsinic acid, oxalic acid, tartrate, oxysuccinic acid, fumaric acid, oleic acid, phenylformic acid, cyclohexane carboxylic acid, phenylbutyric acid, toluic acid, phthalic acid, m-phthalic acid, terephthalic acid, p-methylphenyl sulfonic acid, mandelic acid, mellitic acid, styracin etc.These can use separately also and can two or more mixing use.
As can fluorine, chlorine, bromine, iodine being arranged with the halogen of these aliphatics or aromatic carboxylic acid mixing use.
In the halogenide of above-mentioned aliphatics or aromatic carboxylic acid, when considering to the solvability of organic multiple isocyanate (A1), the isocyanate group terminal amino group manthanoate prepolymer (A) that obtains thus and organic solvent (B) etc., the preferred halogenide that uses aromatic carboxylic acid especially preferably uses phthalyl chloride, phthalyl dichloro, fluorobenzoic acid etc.
The preferably above-mentioned relatively organic multiple isocyanate of the addition of etheride (C) (A1) is 0.00003～5.0 quality %, preferred especially 0.00005～1 quality %.Undoubtedly the interpolation time of etheride (C) is in the front and back of organic multiple isocyanate (A1) and polyvalent alcohol (A2) reaction.
Polyisocyanate solution preparation method of the present invention, be not particularly limited, can adopt and prepare isocyanate group terminal amino group manthanoate prepolymer (A) in advance afterwards, to the method that wherein cooperates organic solvent (B), with the method that in the presence of organic solvent (B), cooperates isocyanate group terminal amino group manthanoate prepolymer (A) etc., can suitably select according to the raw material that uses etc.
Cooperate under the situation of etheride (C), can adopt and prepare isocyanate group terminal amino group manthanoate prepolymer (A) in advance afterwards, to the method that wherein cooperates etheride (C) and organic solvent (B), with in the presence of etheride (C) preparation isocyanate group terminal amino group manthanoate prepolymer (A) afterwards, cooperate the method for organic solvent (B) etc., also can suitably select in this case according to the raw material that uses etc.
In the organic multiple isocyanate solution of above explanation, when making organic multiple isocyanate (A1) and polyvalent alcohol (A2) react (below be called urethane reaction), the equivalence ratio of isocyanate group and hydroxyl (isocyanate group/hydroxyl) preferred 1.5～500, preferred especially 2～400.The temperature of reaction of urethane reaction is preferred 30～120 ℃ in addition, preferred especially 50～100 ℃.
During the urethane reaction, can use urethane catalyzer such as known tertiary amine series catalysts or metal series catalysts, organic multiple isocyanate (A1) and polyvalent alcohol (A2) integral body are 0.01～20 quality % to its addition relatively usually.
Above-mentioned tertiary amine series catalysts for example has: triethylamine, three second, two support diamines, N-methylmorpholine, N-Methylimidazole, 1-Methylimidazole, 1-ethyl imidazol(e), 1-propyl imidazole, 1-cyano group imidazoles, 1-cyano methyl imidazoles, 1,2-methylimidazole, 1,4-methylimidazole, 1-methyl-2-ethyl imidazol(e), 1-methyl-4-ethyl imidazol(e), 1-ethyl-glyoxal ethyline, 1-ethyl-4-methylimidazole, pyridine, α-Jia Jibiding etc.
Above-mentioned metal series catalysts for example has: dibutyltin dilaurate, dioctyl tin dilaurate, calcium naphthenate, potassium octanoate, stannous octoate, zinc octoate etc.
Reduce effect in order to reach color, can add organophosphite based compound, phenol system compound etc. in the polyisocyanate solution of the present invention.
The organophosphite based compound is not particularly limited, for example have: triaryl phosphates such as triphenyl, (2) alkyl diaryl phosphate of alkyl carbon number 4～20, three (2,4-two-tert-butyl-phenyl) phosphoric acid ester, two (2,6-two-tertiary butyl-4-aminomethyl phenyl) end capped tris phosphite of alkyl with two (tertiary butyl) phenyl structure of at least 1 of the phosphorous acid base Sauerstoffatom of pentaerythritol phosphate etc. etc. is bonded in alkyl carbon atom on the Sauerstoffatom of phosphorous acid base to add up to each phosphorous acid base is 12～60 tris phosphite, the tetrabutyl-4, have 2 phosphorous acid bases in 1 molecule of 4-isopropylidene phenylbenzene bisphosphate etc., the skeleton of bonding phosphorous acid base is the material of structure of bisphenol A, the diiso decyl pentaerythritol diphosphate, have 2 or 4 phosphorous acid bases in 1 molecules such as tetraphenyl four decyl tetramethylolmethanes four phosphoric acid ester, the skeleton of bonding phosphorous acid base is the material of tetramethylolmethane structure.
Above-mentioned phosphate compound can use separately also can mix use more than 2 kinds.When the alkyl carbonatoms of bonding added up to 11 in each phosphorous acid base following on the phosphorous acid base Sauerstoffatom, because boiling point is low, volatilization easily prevented that sometimes coloring effect is poor in the polycondensation MDI process.Use the occasion of these organic phosphorous acid ester cpds preferably to share phenol system compound (oxidation inhibitor) for this reason.
Phenol system compound is not particularly limited, for example have: two [2-hydroxy-5-methyl base-3-tert-butyl-phenyl] methane, 2, two [4-hydroxy phenyl] propane of 2-, 4,4 '-dihydroxybiphenyl, 3,3 '-dialkyl group-, or 3,3 ', 5,5 '-tetraalkyl-4,4 '-dihydroxybiphenyl, two [4-hydroxy-2-methyl-5-tert-butyl-phenyl] sulfide, Resorcinol, 2,5-two-Tert. Butyl Hydroquinone, 2,5-two-tert-pentyl Resorcinol, the 4-methoxyphenol, uncle's 4-fourth oxy phenol, 4-benzyloxy phenol, 4-methoxyl group-2-, or-the 3-tert.-butyl phenol, 2,5-dihydroxyl-1-tert.-butylbenzene, 4-methoxyl group-2,6-two-tert.-butyl phenol, 2,6-two-tertiary butyl-p-cresol, 2,6-two-tertiary butyl-4-methylphenol (following abbreviation BHT), list or two or three (Alpha-Methyl phenmethyl) phenol, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-butylidene two (6-t-butyl-3-methylphenol) etc.
The relative isocyanic ester of the addition of above-mentioned bi-ester of phosphite or oxybenzene compound is 0.0010～1 weight %, preferred especially 0.0050～0.5 quality %.Its interpolation is not particularly limited period, and all it doesn't matter after the beginning before the above-mentioned urethane reaction beginning.
Caking agent that the present invention relates to and coating use the polyisocyanate solution of the invention described above, and saying more specifically used as stiffening agent with above-mentioned polyisocyanate solution.
General caking agent and coating are roughly divided into 1 liquid type and 2 liquid types.1 liquid type, be material with the isocyanate group in the above-mentioned polyisocyanate solution of end-capping reagent end-blocking as the potentiality stiffening agent, this stiffening agent is engaged in type as the multi-hydroxy compound of host in advance; Perhaps use above-mentioned polyisocyanate solution to carry out the type of moisture-curable separately.2 liquid types as stiffening agent, cooperate this stiffening agent and as the multi-hydroxy compound of host with above-mentioned polyisocyanate solution before be about to using.
Caking agent and coating type among the present invention are not particularly limited, and the above-mentioned polyisocyanate solution of preferred especially use wherein is used 2 liquid types as the multi-hydroxy compound of host as stiffening agent.
The multi-hydroxy compound that uses as host also can use above-mentioned polyvalent alcohol (A2), characteristics such as the cementability of giving when considering (stopping property), rerum natura, weather resistance as caking agent and coating, the preferred material that uses intramolecularly to have the number-average molecular weight 500～100,000 of 2 above hydroxyls.
These compounds specifically for example have: saturated or unsaturated polyester ester polyol, polycaprolactone polyol, saturated or unsaturated oil modification or fatty acid modified Synolac polyvalent alcohol, the amino-alkyd resin polyvalent alcohol, polycarbonate polyol, acrylic polyol, polyether glycol, epoxy polyol, fluorine-containing polyvalent alcohol, saturated or unsaturated polyester resin, the polycaprolactone resin, saturated or unsaturated oil modification or fatty acid modified Synolac, amino-alkyd resin, polycarbonate resin, acrylic resin, polyether resin, Resins, epoxy, urethane resin, rhodia butyric ester resin, fluorine resin etc.
Characteristics such as the cementability (stopping property) when considering, rerum natura, weather resistance as caking agent and coating, in above-mentioned caking agent and the coating, preferred 9: 1～1: 9 of the mol ratio of the hydroxyl in isocyanate group in the polyisocyanate solution and the multi-hydroxy compound in the host, preferred especially 7: 3～3: 7.
When using applying coating of the present invention, can use existing common coating method, for example can use following method to apply: applications such as airless paint spraying machine, air paint spraying machine, electrostatic atomizer, dipping, roller coating, blade coating, hairbrush.
Can be used aforementioned urethane catalyst as required in caking agent of the present invention and the coating.In this case, preferred 0.01～20 quality % of the above-mentioned relatively isocyanate group terminal amino group of catalyzer addition manthanoate prepolymer (A).Addition is during less than 0.01 quality %, and sclerous reaction is insufficient, and the anxiety of the purpose of can not get product is arranged, and in addition, when surpassing 20 quality %, for caking agent or coating, exists to change the danger that cementability (stopping property), rerum natura reduce in time.
Can suitably cooperate inorganic filler such as cement, blast furnace slag, gypsum, lime carbonate, clay, aluminium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, unslaked lime, slaked lime, bentonite or be coated with various pigment commonly used in flat agent, fire retardant, anti-aging agent, thermotolerance toughener, oxidation inhibitor, other the paint industry and various additives etc., also can suitably regulate its use level as required.
As mentioned above, organic isocyanate solution of the present invention is because be the polyisocyanate solution that contains the isocyanate group terminal amino group manthanoate prepolymer (A) and the organic solvent (B) of regulation, so have consistency, hardness and the drying property of good hardening, solvent solubility and other resin simultaneously.In these (A), (B) each composition, cooperate etheride (C) again, be difficult to produce because viscosity increases, solvent solubility or with the consistency reduction of other resin etc. over time, can make the polyisocyanate solution that has excellent storage stability,
These polyisocyanate solution as stiffening agent, can be obtained the caking agent and the coating thereof of characteristic goods such as hardness, cementability and stopping property thus.
Below by embodiment and comparative example specific description the present invention more, but the invention is not restricted to these embodiment.
[1] preparation 1 of polyisocyanate solution
Embodiment 1～5
To the capacity 1000ml or 3 that has stirrer, thermometer, reflux exchanger and nitrogen ingress pipe, in the reactor of 000ml, add each organic multiple isocyanate (A1), the polyvalent alcohol (A2) of the use level shown in the table 1.Be heated to 70～80 ℃ while stirring, make its urethane reaction proceed to target NCO content (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)).Under 120～140 ℃, 1～5Pa, remove unreacted TDI in the reaction solution afterwards, residual free TDI content is reached below the 0.5 quality % by thin film distillation.
Add the organic solvent (B) of use level shown in the table 1 in the solution after the thin film distillation, obtain polyisocyanate solution P-1～5.
Comparative example 1～5,10～13,15
Add organic multiple isocyanate (A1), polyvalent alcohol (A2) with use level shown in the table 2, make itself and embodiment 1 carry out urethane reaction (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)) and thin film distillation in the same manner, add organic solvent (B) with the use level shown in the table 2 afterwards, obtain polyisocyanate solution P-6～10, P-15～18, P-20.
Comparative example 6～9,14
Add organic multiple isocyanate (A1), polyvalent alcohol (A2) with use level shown in the table 2, make itself and embodiment 1 carry out urethane reaction (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)) in the same manner, add organic solvent (B) with the use level shown in the table 2 afterwards, obtain polyisocyanate solution P-11～14, P-19.
Each polyisocyanate solution that obtains for the various embodiments described above and comparative example at table 1, shows isocyanate content and solid ingredient amount in 2 in the lump.
Table 1
| Embodiment | |||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |||
| Organic multiple isocyanate (g) | コ ロ ネ one ト T-100 | ????900 | ????- | ????- | ????- | ????- | |
| コ ロ ネ one ト T-80 | ????- | ????900 | ????900 | ????- | ????- | ||
| コ ロ ネ one ト T-65 | ????- | ????- | ????- | ????900 | ????900 | ||
| Polyvalent alcohol (g) | ????TMP | ????49 | ????45 | ????48 | ????47 | ????32 | |
| ????Gly | ????12 | ????16 | ????21 | ????15 | ????25 | ||
| ????EG | ????- | ????- | ????- | ????5 | ????5 | ||
| ????1，3-BD | ????14 | ????10 | ????- | ????22 | ????- | ||
| ????PRD | ????25 | ????- | ????15 | ????11 | ????18 | ||
| ????PND | ????- | ????- | ????- | ????- | ????15 | ||
| ????DPG | ????- | ????29 | ????- | ????- | ????5 | ||
| ????PP-400 | ????- | ????- | ????16 | ????- | ????- | ||
| Organic solvent (g) | Toluene | ????500 | ????- | ????- | ????- | ????750 | |
| Dimethylbenzene | ????- | ????- | ????125 | ????- | ????- | ||
| Vinyl acetic monomer | ????- | ????333 | ????- | ????333 | ????- | ||
| Methyl ethyl ketone | ????500 | ????- | ????125 | ????- | ????750 | ||
| ????????????f2 | ????39 | ????30 | ????21 | ????38 | ????39 | ||
| ????????????f3 | ????61 | ????70 | ????79 | ????62 | ????61 | ||
| The G value | ????16 | ????24 | ????31 | ????20 | ????32 | ||
| The polyisocyanate solution title | ????P-1 | ????P-2 | ????P-3 | ????P-4 | ????P-5 | ||
| Synthetic post analysis value | Isocyanate content (%) | ????8.7 | ????13.3 | ????14.8 | ????13.3 | ????6.5 | |
| Solids component (%) | ????50 | ????75 | ????80 | ????75 | ????40 | ||
Table 2
| Comparative example | ||||||||||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 | ??15 | ||
| Organic multiple isocyanate (g) | コ D ネ one ト T-100 | ??900 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? |
| コ ロ ネ one ト T-80 | ??- ? | ??890 ? | ??796 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??900 ? | ??930 ? | ??908 ? | ??920 ? | ??- ? | ??- ? | |
| コ ロ ネ one ト T-65 | ??- ? ? | ??- ? ? | ??- ? ? | ??900 ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??- ? ? | ??900 ? ? | |
| ??HDI | ??- | ??- | ??- | ??- | ??900 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| ミ リ エ ネ one ト MTL | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??900 ? | ??930 ? | ??908 ? | ??920 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??900 ? | ??- ? | |
| Polyvalent alcohol (g) | ??TMP | ??40 | ??25 | ??204 | ??40 | ??25 | ??30 | ??- | ??31 | ??45 | ??30 | ??- | ??31 | ??45 | ??30 | ??30 |
| ??Gly | ??5 | ??65 | ??- | ??4 | ??8 | ??32 | ??40 | ??5 | ??3 | ??32 | ??40 | ??5 | ??3 | ??15 | ??15 | |
| ??EG | ??5 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| ??1，3-BD | ??40 | ??5 | ??- | ??10 | ??20 | ??18 | ??15 | ??10 | ??10 | ??18 | ??15 | ??10 | ??10 | ??18 | ??18 | |
| ??PRD ? | ??- ? | ??- ? | ??- ? | ??- ? | ??20 ? | ??20 ? | ??15 ? | ??- ? | ??10 ? | ??20 ? | ??15 ? | ??- ? | ??10 ? | ??20 ? | ??20 ? | |
| ??PND | ??- | ??10 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| ??DPG | ??10 | ??5 | ??- | ??- | ??27 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??17 | ??17 | |
| ??PP-400 | ??- | ??- | ??- | ??46 | ??- | ??- | ??- | ??46 | ??12 | ??- | ??- | ??46 | ??12 | ??- | ??- | |
| Organic solvent (g) | Toluene | ??500 | ??- | ??- | ??- | ??500 | ??- | ??- | ??- | ??- | ??100 | ??100 | ??100 | ??100 | ??- | ??100 |
| Vinyl acetic monomer | ??- | ??333 | ??1000 | ??333 | ??- | ??333 | ??333 | ??333 | ??333 | ??233 | ??233 | ??233 | ??233 | ??333 | ??- | |
| Methyl ethyl ketone | ??500 | ??- | ??1333 | ??- | ??500 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??233 | |
| ??????????????f2 | ??53 | ??14 | ??0 | ??31 | ??63 | ??35 | ??36 | ??35 | ??33 | ??35 | ??36 | ??35 | ??33 | ??50 | ??50 | |
| ??????????????f3 | ??47 | ??86 | ??100 | ??69 | ??37 | ??65 | ??64 | ??65 | ??67 | ??65 | ??64 | ??65 | ??67 | ??50 | ??50. | |
| The G value | ??7 | ??68 | ??0 | ??9 | ??12 | ??40 | ??64 | ??12 | ??6 | ??40 | ??64 | ??12 | ??6 | ??21 | ??21 | |
| The polyisocyanate solution title | ??P-6 | ??P-7 | ??P-8 | ??P-9 | ??P-10 | ??P-11 | ??P-12 | ??P-13 | ??P-14 | ??P-15 | ??P-16 | ??P-17 | ??P-18 | ??P-19 | ??P-20 | |
| Synthetic post analysis value | Isocyanate content (%) | ??9.0 | ??11.7 | ??* | ??15.1 | ??9.1 | ??24.3 | ??27.3 | ??28.7 | ??28.1 | ??12.2 | ??13.9 | ??15.1 | ??14.5 | ??25.2 | ??13.3 |
| Gu shape branch (%) | ??50 | ??75 | ??* | ??75 | ??50 | ??75 | ??75 | ??75 | ??75 | ??75 | ??75 | ??75 | ??75 | ??75 | ??75 | |
* can't measure owing to bad order
Above-mentioned table 1, in 2, f2 represents to have in 1 molecule mole % of all relatively polyvalent alcohols of polyvalent alcohol of 2 alcoholic hydroxyl, and f3 represents to have in 1 molecule mole % of all relatively polyvalent alcohols of polyvalent alcohol of 3 alcoholic hydroxyl, and G value representation glycerol is with respect to the mole % of all polyvalent alcohols.
Other trade(brand)name, be called for short as follows in detail.
コ ロ ネ-ト T-100 (Japanese polyurethane industry (strain) system): 2,4-TDI
コ ロ ネ-ト T-80 (Japanese polyurethane industry (strain) system): 2,4-TDI and 2, the mixture of 6-TDI (2,4-TDI/2,6-TDI=80/20 (mass ratio))
コ ロ ネ-ト T-80 (Japanese polyurethane industry (strain) system): 2,4-TDI and 2, the mixture of 6-TDI (2,4-TDI/2,6-TDI=80/20 (mass ratio))
コ ロ ネ-ト T-65 (Japanese polyurethane industry (strain) system): 2,4-TDI and 2, the mixture of 6-TDI (2,4-TDI/2,6-TDI=65/35 (mass ratio))
TDI: hexamethylene diisocyanate
ミ リ オ ネ-ト MTL: carbodiimide modified version MDI (Japanese polyurethane industry (strain) system)
TMP: TriMethylolPropane(TMP) (functional group's number=3)
Gly: glycerol (functional group's number=3)
1,3-BD:1,3-butyleneglycol (functional group's number=2)
EG: ethylene glycol
PRD:1,2-propylene glycol (functional group's number=2)
PND:1,5-pentanediol (functional group's number=2)
PP-400 (Sanyo changes into industry (strain) system): poly-(oxypropylene) polyvalent alcohol, specified functional group number=2, number-average molecular weight=400
コ ロ ネ-ト is the registered trademark of a kind of Japanese polyurethane industry (strain), and ミ リ オ ネ-ト is the registered trademark (industry of permission Japanese polyurethane is used) of hodogaya chemical industry (strain).
The polyisocyanate solution that the various embodiments described above and comparative example obtain records the viscosity after the firm preparation, is shown in table 3.
Use the Canon Off エ Application ス ケ viscometer of regulation to measure viscosity according to JIS K 2283-1980.
Polyisocyanates is to carry out solvent cut according to its application target, needs to use mostly, records, estimates the solvent solubility of above-mentioned each polyisocyanate solution, is shown in table 3 in the lump.
The mensuration of solvent solubility and evaluation are undertaken by following method.
The solvent solubility test
Get polyisocyanate solution 5g, utilize drop-burette progressively to add toluene slightly, shake well is defined as terminal point when muddiness occurring, tries to achieve the ml of required solvent this moment.Utilize following formula to try to achieve solvent solubility (doubly) then.Its value is big more, and solvent solubility is good more.
Ml number/the sample size (5g) of solvent solubility (doubly)=required solvent
Table 3
| The solution title | After synthetic | ||
| Viscosity (25 ℃) (mm 2/s) | Solvent solubility (doubly) | ||
| Embodiment 1 | ?P-1 | ????7 | ????38 |
| Embodiment 2 | ?P-2 | ????1290 | ????43 |
| Embodiment 3 | ?P-3 | ????3200 | ????35 |
| Embodiment 4 | ?P-4 | ????1280 | ????45 |
| Embodiment 5 | ?P-5 | Below 5 | ????40 |
| Comparative example 1 | ?P-6 | ????10 | ????15 |
| Comparative example 2 | ?P-7 | ????1500 | ????9 |
| Comparative example 3 | ?P-8 | ????* | ????* |
| Comparative example 4 | ?P-9 | ????780 | ????13 |
| Comparative example 5 | ?P-10 | ????5 | ????23 |
| Comparative example 6 | ?P-11 | ????2100 | ????6 |
| Comparative example 7 | ?P-12 | ????1300 | ????8 |
| Comparative example 8 | ?P-13 | ????1000 | ????9 |
| Comparative example 9 | ?P-14 | ????1100 | ????8 |
| Comparative example 10 | ?P-15 | ????1450 | ????11 |
| Comparative example 11 | ?P-16 | ????1020 | ????10 |
| Comparative example 12 | ?P-17 | ????790 | ????13 |
| Comparative example 13 | ?P-18 | ????900 | ????11 |
| Comparative example 14 | ?P-19 | ????1700 | ????6 |
| Comparative example 15 | ?P-20 | ????1100 | ????11 |
* can't measure owing to bad order
As shown in table 3, the polyisocyanate solution that as seen contains the embodiment 1～5 of the isocyanate group terminal amino group manthanoate prepolymer (A) of the present invention regulation and organic solvent (B) has good solvent solubility.Relatively example 1～15, and the solvent solubility of visible polyisocyanate solution is low.
Utilize following method, carry out the compatibility test of other resin of above-mentioned relatively each polyisocyanate solution.
Compatibility test
Mix above-mentioned each polyisocyanate solution with the various resins shown in table 4 and the table 5 at 1: 1 with mass ratio, the mixed solution that obtains is coated on the sheet glass, made complete solvent evaporates in 120 ℃ through 1 hour afterwards, the appearance of film below estimating according to following judgement criteria.The result is shown in Table 4 in the lump.
Zero: transparent, △: have a little mist, *: opaque.
Table 4
| Consistency with other resin | Embodiment | |||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ||
| After synthetic | ニツポラン1100 | ????○ | ????○ | ????○ | ????○ | ????○ |
| アクリデイツクA-801 | ????○ | ????○ | ????○ | ????○ | ????○ | |
| Nitro-cotton | ????○ | ????○ | ????○ | ????○ | ????○ | |
| Vinylchlorid-vinyl-acetic ester | ????○ | ????○ | ????○ | ????○ | ????○ | |
| CAB | ????○ | ????○ | ????○ | ????○ | ????○ | |
ニ Star Port ラ Application 1100: Japanese polyurethane industry system polyester polyol
ア Network リ デ イ Star Network A-801: big Japanese ink chemical industry (strain) system acrylate copolymer
Nitro-cotton: Asahi Chemical Industry's industry (strain) system nitro-cotton セ Le ノ バ BTH 1/2
Vinylchlorid-vinyl-acetic ester: ponding chemical industry preparing chloroethylene-vinyl acetate copolymer.
CAB:Eastman chemistry (strain) system cellulose acetate butyrate
Table 5
| Count the consistency of resin with other | Comparative example | |||||||||||||||
| ??1 ? | ??2 ? | ??3 ? | ??4 ? | ??5 ? | ??6 ? | ??7 ? | ??8 ? | ??9 ? | ??10 ? | ??11 ? | ??12 ? | ??13 ? | ??14 ? | ??15 ? | ||
| After synthetic | ??ニツポラン ??1100 | ??○ ? | ??△ ? | ??* ? | ??○ ? | ??○ ? | ??△ ? | ??○ ? | ??○ ? | ??○ ? | ??△ ? | ??△ ? | ??○ ? | ??○ ? | ??△ ? | ??△ ? |
| ??アクリデイツ ? ??クA-801 | ??× ? | ??× ? | ??* ? | ??○ ? | ??○ ? | ??× ? | ??○ ? | ??○ ? | ??○ ? | ??△ ? | ??× ? | ??○ ? | ??○ ? | ??× ? | ??△ ? | |
| Nitro-cotton | ??△ | ??△ | ??* | ??△ | ??△ | ??× | ??△ | ??△ | ??△ | ??△ | ??△ | ??△ | ??△ | ??× | ??△ | |
| Vinylchlorid-vinyl-acetic ester | ??△ ? | ??△ ? | ??* ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | |
| ??CAB | ??△ | ??× | ??* | ??× | ??△ | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | |
* because outward appearance is bad, can not measure
ニ Star Port ラ Application 1100: Japanese polyurethane industry system polyester polyol
ア Network リ デ イ Star Network A-801: big Japanese ink chemical industry (strain) system acrylate copolymer
Nitro-cotton: Asahi Chemical Industry's industry (strain) system nitro-cotton セ Le ノ バ BTH 1/2
Vinylchlorid-vinyl-acetic ester: ponding chemical industry preparing chloroethylene-vinyl acetate copolymer.
CAB:Eastman chemistry (strain) system cellulose acetate butyrate
In addition, ニ Star Port ラ Application is the registered trademark of Japanese polyurethane industry (strain), and セ Le ノ バ is that registered trademark, the ア Network リ デ イ Star Network of Asahi Chemical Industry's industry (strain) is the registered trademark of a kind of big Japanese ink chemical industry (strain).
As table 4, shown in 5, the polyisocyanate solution of embodiment 1～5 preparation and comparative example polyisocyanate solution contrast has good and consistency other resin.
The hardening test
Above-mentioned each isocyanate solution mixes with mol ratio with each resin shown in table 6 and table 7 at 1: 1, becomes solids component=37.5 quality % with solvent cut.And the fluid,matching that will prepare like this is applied as dry film thickness=40～50 μ m in advance with the bonding steel plate after the trieline degreasing, places 3 days under 20 ℃, the atmosphere of 65RH%.Scrape afterwards and get this and film, as solvent, under this boiling point, reflux with methyl ethyl ketone, 20 hours, use apparatus,Soxhlet's to carry out solvent extraction, record the quality of filming before and after the solvent extraction.Use these measured values, utilize following formula to try to achieve gel fraction, utilize this to be worth harder voltinism.The value of this gel fraction is big more, represents that this hardening is good more.
Gel fraction (%)=[film quality (g) before the film quality after the extraction (g)/extraction] * 100
Table 6
| The hardening test | Embodiment | |||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ||
| Polyisocyanate solution (g) | ????P-1 ? ????180 | ????P-2 ? ????119 | ????P-3 ? ????202 | ????P-4 ? ????220 | ????P-5 ? ????372 | |
| Host (g) | ヒロイド 3088 | ????420 ? | ????422 ? | ????- ? | ????- ? | ????- ? |
| ニツポラン 800 | ????- ? | ????- ? | ????138 ? | ????135 ? | ????- ? | |
| ニツポラン 1100 | ????- ? | ????- ? | ????- ? | ????- ? | ????151 ? | |
| Diluting solvent (g) | Toluene | ????100 | ????100 | ????200 | ????200 | ????- |
| Vinyl acetic monomer | ????100 | ????- | ????260 | ????- | ????100 | |
| N-BUTYL ACETATE | ????- | ????159 | ????- | ????245 | ????177 | |
| Gel fraction (%) | ????81 | ????86 | ????92 | ????82 | ????85 | |
Table 7
| The hardening test | Comparative example | ||||||||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 | ||
| Polyisocyanate solution (g) | ??P-6 ??176 | ??P-7 ??233 | ??P-9 ??177 | ??P-10 ??175 | ??P-11 ??132 | ??P-12 ??122 | ??P-13 ??118 | ??P-14 ??120 | ??P-15 ??229 | ??P-16 ??216 | ??P-17 ??208 | ??P-18 ??212 | ??P-19 ??129 | ??P-20 ??220 | |
| Host (g) | ??ヒロイ ??ド3088 | ??424 | ??- | ??- | ??425 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- |
| ??ニツポラ ??ン800 | ??- ? | ??125 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??128 ? | ??138 ? | ??144 ? | ??141 ? | ??- ? | ??135 ? | |
| ??ニツポラ ??ン1100 | ??- ? | ??- ? | ??167 ? | ??- ? | ??201 ? | ??209 ? | ??212 ? | ??210 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??203 ? | ??- ? | |
| Diluting solvent (g) | Toluene | ??100 | ??200 | ??- | ??100 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 |
| Vinyl acetic monomer | ??100 | ??- | ??200 | ??- | ??267 | ??269 | ??270 | ??270 | ??243 | ??246 | ??248 | ??247 | ??268 | ??245 | |
| N-BUTYL ACETATE | ??- | ??242 | ??256 | ??100 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| Gel fraction (%) | ??53 | ??77 | ??62 | ??33 | ??88 | ??94 | ??82 | ??81 | ??70 | ??76 | ??64 | ??60 | ??83 | ??55 | |
At table 6, Details as Follows for the material that each trade(brand)name is represented in 7.
(Hitachi changes into industry (strain) system to ヒ ロ イ De 3088: acrylic polyol, hydroxyl value=50mgKOH/g, solids component=50%
ニ Star Port ラ Application 800 (Japanese polyurethane industry (strain) system: polyester polyol, hydroxyl value=290mgKOH/g, solids component=100%
ニ Star Port ラ Application 1100 (Japanese polyurethane industry (strain) system: polyester polyol, hydroxyl value=213mgKOH/g, solids component=100%
In addition, ヒ ロ イ De is the registered trademark that Hitachi changes into industry (strain).
By table 6,7 as can be known, and the occasion of the polyisocyanate solution that use embodiment 1～5 obtains can be brought into play good hardening.In addition, as seen the occasion of the polyisocyanate solution that use comparative example 1～15 obtains although also wherein have good indurative material, but as table 3, shown in 5, because solvent solubility or poor with the consistency of other resin is not a kind of material that has all characteristics simultaneously.
[2] caking agent estimates 1
[embodiment 6～10, comparative example 16～30]
Polyisocyanate solution P-1～20 that obtained by the foregoing description 1～5 and comparative example 1～15 are as stiffening agent, as host, utilize following method to estimate the caking agent of 2 liquid types with polyurethane resin solution ニ Star Port ラ Application 3016 (Japanese polyurethane industry (strain) system, ethyl acetate solution, hydroxyl amount=0.04mmol/g, solids component=22%) with caking agent.
Hydroxyl and the isocyanate group in the stiffening agent that the proportioning of host and stiffening agent is made in the host are normal ratio.
Adhesive test
Urethane RIM (reaction injection molding(RIM) is molded) molding, FRP, ABS, steel plate (JISG3141 (3141-SB), model: PF-1077, Japanese testing instrument industry system, the bonding steel plate of following abbreviation with length 100mm, wide 25mm, thickness 1mm.) use the trieline degreasing, the adhesive applicating that cooperates above-mentioned host/stiffening agent on it and form is become dry film thickness 40～50 μ m, surface covered 25mm * 25mm.
50 ℃ of down dry 5 minutes of preparations, the solvent in the evaporation caking agent does not enter bubble, and 2 of above-mentioned each plates of same kind is overlapping then, compresses with 2.5Mpa, and it was placed 3 days in 20 ℃, the atmosphere of 65%RH, obtains bonding sample.
Thereafter, at draw speed=100mm/min, measure under the condition of atmosphere=23 ℃, 50%RH and record bonding shearing strength.The results are shown in table 8,9.
Table 8
| Adhesive test | Embodiment | ||||||
| ??6 | ??7 | ??8 | ??9 | ??10 | |||
| The polyisocyanate solution title | ??P-1 | ??P-2 | ??P-3 | ??P-4 | ??P-5 | ||
| After synthetic | By convered structure | ??RIM/RIM | ??20/A | ??18/A | ??17/A | ??20/A | ??20/A |
| ??FRP/FRP | ??14/A | ??15/A | ??13/A | ??14/A | ??13/A | ||
| ??ABS/ABS | ??17/A | ??17/A | ??15/A | ??17/A | ??16/A | ||
| Bonded steel/bonded steel | ??16/A ? | ??20/A ? | ??18/A ? | ??21/A ? | ??19/A ? | ||
Method for expressing: bonding strength (MPa)/collapse state
Collapse state A: aggegation destroys
Table 9
| Then property test | Comparative example | ||||||||||||||||
| 16 | 17 | ???18 | 19 | ?20 | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | |||
| Polyisocyanate solution: title | P-6 | P-7 | ???P-8 | P-9 | ?P-10 | P-11 | P-12 | P-13 | P-14 | P-15 | P-16 | P-17 | P-18 | P-19 | P-20 | ||
| After synthetic | By convered structure | ??RIM/RIM | 14/A | 15/A | ????* | 18/A | ?6/A | 14/A | 14/A | 13/A | 14/A | 18/A | 17/A | 15/A | 17/A | 13/A | 14/A |
| ??FRP/FRP | 11/A | 15/A | ????* | 15/A | ?4/A | 10/A | 9/A | 8/A | 9/A | 16/A | 15/A | 14/A | 15/A | 10/A | 13/A | ||
| ??ABS/ABS ? | 13/A ? | 16/A ? | ????* ? | 16/A ? | ?4/A ? | 10/A ? | 11/A ? | 11/A ? | 11/A ? | 18/A ? | 17/A ? | 18/A ? | 17/A ? | 10/A ? | 13/A ? | ||
| Bonded steel/bonded steel | 12/A ? | 18/A ? | ????* ? | 17/A ? | ?6/A ? | 16/A ? | 15/A ? | 16/A ? | 16/A ? | 17/A ? | 18/A ? | 15/A ? | 17/A ? | 16/A ? | 14/A ? | ||
* because outward appearance is bad, can not measure
Method for expressing: bonding strength (MPa)/collapse state
Collapse state A: aggegation destroys
As table 8, shown in 9, the polyisocyanate solution that embodiment 1～5 is obtained also has the significantly high bonding strength to various materials as the caking agent that the caking agent of the embodiment 6～10 of stiffening agent obtains than comparative example 16～30.
[3] coating assessment 1
Embodiment 11～15, comparative example 31～44
Polyisocyanate solution as stiffening agent uses the foregoing description 1～5 and comparative example 1,2,4～15 to obtain fits in as table 10, shown in 11, cooperates mix polyisocyanate solution and other each coating raw materials, fits in coating.
The applying coating that cooperates like this on the bonding steel plate by the trieline degreasing, was placed 3 under 20 ℃, the environment of 65%RH, formed dry film thickness=40～50 μ m.And each rerum natura of filming that forms is measured, is estimated according to the method for JIS K5400.The results are shown in table 12, in 13.
Table 10, the material that each trade(brand)name is represented in 11 in detail as mentioned above.
Table 10
| Be coated with film test | Embodiment | |||||
| ????11 | ????12 | ????13 | ????14 | ????15 | ||
| Polyisocyanate solution (g) | ????P-1 ????180 | ????P-2 ????119 | ????P-3 ????202 | ????P-4 ????220 | ????P-5 ????372 | |
| Host (g) | ??ヒロイド ??3088 | ????420 | ????422 | ????- | ????- | ????- |
| ??ニツポラン ??800 | ????- | ????- | ????138 | ????135 | ????- | |
| ??ニツポラン ??1100 | ????- | ????- | ????- | ????- | ????151 | |
| Diluting solvent (g) | Toluene | ????100 | ????100 | ????200 | ????200 | ????- |
| Vinyl acetic monomer | ????100 | ????- | ????260 | ????- | ????100 | |
| N-BUTYL ACETATE | ????- | ????159 | ????- | ????245 | ????177 | |
| Pigment (g) | Titanium oxide | ????200 ? | ????200 ? | ????200 ? | ????200 ? | ????200 ? |
Table 11
| Be coated with film test | Comparative example | ||||||||||||||
| ??31 | ??32 | ??33 | ??34 | ??35 | ??36 | ??37 | ??38 | ??39 | ??40 | ??41 | ??42 | ??43 | ??44 | ||
| Polyisocyanate solution (g) | ??P-6 ??176 | ??P-7 ??233 | ??P-9 ??177 | ??P-10 ??175 | ??P-11 ??132 | ??P-12 ??122 | ??P-13 ??118 | ??P-14 ??120 | ??P-15 ??229 | ??P-16 ??216 | ??P-17 ??208 | ??P-18 ??212 | ??P-19 ??129 | ??P-20 ??220 | |
| Host (g) | ??ヒロイ ??ド3088 | ??424 ? | ??- ? | ??- ? | ??425 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? |
| ??ニツポラ ??ン800 | ??- | ??125 | ??- | ??- | ??- | ??- | ??- | ??- | ??128 | ??138 | ??144 | ??141 | ??- | ??135 | |
| ??ニツポラ ??ン1100 | ??- | ??- | ??167 | ??- | ??201 | ??209 | ??212 | ??210 | ??- | ??- | ??- | ??- | ??203 | ??- | |
| Diluting solvent (g) | Toluene | ??100 | ??200 | ??- | ??100 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 |
| Vinyl acetic monomer | ??100 | ??- | ??200 | ??- | ??267 | ??269 | ??270 | ??270 | ??243 | ??246 | ??248 | ??247 | ??268 | ??245 | |
| N-BUTYL ACETATE | ??- | ??242 | ??256 | ??100 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| Pigment (g) | Titanium oxide | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? |
Table 12
| Be coated with film test | Embodiment | ||||||
| ????11 | ????12 | ????13 | ????14 | ????15 | |||
| After synthetic | Gloss | ????91 | ????90 | ????89 | ????87 | ????90 | |
| Drying property | Touch dry (branch) | ????21 ? | ????23 ? | ????55 ? | ????60 ? | ????58 ? | |
| Dry through (branch) | ????45 ? | ????48 ? | ????130 ? | ????145 ? | ????140 ? | ||
| The impact of デ ユ Port Application (1/2 ", 500g) (cm) | ????100 ? | ????110 ? | ????100 ? | ????100 ? | ????110 ? | ||
| Flexibility (2mm φ) | Qualified | Qualified | Qualified | Qualified | Qualified | ||
| Sven-Gan Eriksson value (mm) | ????9 | ????10 | ????8 | ????10 | ????8 | ||
| Pencil hardness | ????H | ????H | ????F | ????F | ????F | ||
| Stopping property (point) | ????10 ? | ????10 ? | ????10 ? | ????10 ? | ????10 ? | ||
Table 13
| Be coated with film test | Comparative example | |||||||||||||||
| ??31 | ??32 | ??33 | ??34 | ??35 | ??36 | ??37 | ??3.3 | ??39 | ??40 | ??41 | ??42 | ??43 | ??44 | |||
| After synthetic | Gloss | ??92 | ??91 | ??91 | ??90 | ??76 | ??77 | ??78 | ??77 | ??92 | ??91 | ??90 | ??91 | ??76 | ??92 | |
| Drying property | Touch dry (branch) | ??85 ? | ??52 ? | ??80 ? | ??230 ? | ??180 ? | ??160 ? | ??130 ? | ??170 ? | ??75 ? | ??68 ? | ??70 ? | ??69 ? | ??170 ? | ??90 ? | |
| Dry through (branch) | ??170 ? | ??110 ? | ??160 ? | ??≥500 ? | ??380 ? | ??350 ? | ??290 ? | ??360 ? | ??180 ? | ??155 ? | ??160 ? | ??150 ? | ??370 ? | ??180 ? | ||
| The impact of デ ユ Port Application (1/2 ", 500g) (cm) | ??≥150 ? ? | ??90 ? ? | ??100 ? ? | ??≥150 ? ? | ??≥150 ? ? | ??≥150 ? ? | ??≥150 ? ? | ??≥150 ? ? | ??100 ? ? | ??90 ? ? | ??100 ? ? | ??90 ? ? | ?≥150 ? ? | ?≥150 ? ? | ||
| Bendability (2mm φ) | Defective | Qualified | Qualified | Defective | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Defective | ||
| Sven-Gan Eriksson value (mm) | ??≥12 | ??9 | ??10 | ??≥12 | ??≥12 | ??≥12 | ??≥12 | ??≥12 | ??8 | ??9 | ??8 | ??9 | ??≥12 | ??≥12 | ||
| Pencil hardness | ??B | ??B | ??B | ??2B | ??3 | ??B | ??B | ??B | ??B | ??B | ??B | ??B | ??B | ??B | ||
| Adherence (point) | ??6 | ??7 | ??7 | ??7 | ??9 | ??9 | ??9 | ??9 | ??7 | ??8 | ??7 | ??7 | ??8 | ??6 | ||
As table 12, shown in 13, the polyisocyanate solution that embodiment 1～5 obtains is compared with the coating of comparative example 31～44 as the coating among the embodiment 11～15 of stiffening agent, has each good film performance, has each characteristic such as good stopping property, hardness and drying property especially.
[4] preparation 2 of polyisocyanate solution
[embodiment 16～19]
To the capacity 1000ml or 3 that has stirrer, thermometer, reflux exchanger and nitrogen ingress pipe, in the reactor of 000ml, add each organic multiple isocyanate (A1), polyvalent alcohol (A2) and the etheride (C) of the use level shown in the table 14.Be heated to 70～80 ℃ while stirring, make its urethane reaction proceed to target NCO content (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)).Afterwards under 120～140 ℃, 1～5Pa by thin film distillation, remove unreacted TDI in the reaction solution, residual free TDI content is reached below the 0.5 quality %.
Add the organic solvent (B) of use level shown in the table 14 in the solution after the thin film distillation, obtain polyisocyanate solution P-21～24.
Embodiment 20
Add organic multiple isocyanate (A1) and polyvalent alcohol (A2) with the use level shown in the table 14, make itself and embodiment 16 carry out urethane reaction (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)) in the same manner, after the thin film distillation, add etheride (C) in the solution that obtains with the use level shown in the table 14, add organic solvent (B) with the use level shown in the table 14 again, obtain polyisocyanate solution P-25.
Comparative example 45～49,54～57,59
Add each organic multiple isocyanate (A1), polyvalent alcohol (A2) and stabilization agent with the use level shown in the table 15, make it carry out urethane reaction (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)) equally with embodiment 16, add organic solvent (B) with the use level shown in the table 15 afterwards, obtain polyisocyanates P-26～30, P35～38, P-40.
Comparative example 50～53,58
Add each organic multiple isocyanate (A1), polyvalent alcohol (A2) and stabilization agent with the use level shown in the table 15, make it carry out urethane reaction (synthesizing of isocyanate group terminal amino group manthanoate prepolymer (A)) equally with embodiment 16, add organic solvent (B) with the use level shown in the table 15 afterwards, obtain polyisocyanates P-31～34, P-39.
In each polyisocyanate solution that the various embodiments described above and comparative example obtain, isocyanate content and solids component are shown in the table 14,15 in the lump.
Table 14
| Embodiment | |||||||
| ????16 | ????17 | ????18 | ????19 | ????20 | |||
| Organic multiple isocyanate (g) | ??コロネ-トT-100 | ????900 | ????- | ????- | ????- | ????- | |
| ??コロネ-トT-80 | ????- | ????900 | ????900 | ????- | ????- | ||
| ??コロネ-トT-65 | ????- | ????- | ????- | ????900 | ????900 | ||
| Polyvalent alcohol (g) | ????TMP | ????49 | ????45 | ????48 | ????47 | ????32 | |
| ????Gly | ????12 | ????16 | ????21 | ????15 | ????25 | ||
| ????EG | ????- | ????- | ????- | ????5 | ????5 | ||
| ????1，3-BD | ????14 | ????10 | ????- | ????22 | ????- | ||
| ????PRD | ????25 | ????- | ????15 | ????11 | ????18 | ||
| ????PND | ????- | ????- | ????- | ????- | ????15 | ||
| ????DPG | ????- | ????29 | ????- | ????- | ????5 | ||
| ????PP-400 | ????- | ????- | ????16 | ????- | ????- | ||
| Etheride (g) | ????PAC | ????0.1 | ????0.1 | ????- | ????- | ????0.1 | |
| ????FBA | ????- | ????- | ????0.1 | ????0.1 | ????- | ||
| Organic solvent (g) | Toluene | ????500 | ????- | ????- | ????- | ????750 | |
| Dimethylbenzene | ????- | ????- | ????125 | ????- | ????- | ||
| Vinyl acetic monomer | ????- | ????333 | ????- | ????333 | ????- | ||
| Methyl ethyl ketone | ????500 | ????- | ????125 | ????- | ????750 | ||
| ??????????????f2 | ????39 | ????30 | ????21 | ????38 | ????39 | ||
| ??????????????f3 | ????61 | ????70 | ????79 | ????62 | ????61 | ||
| The G value | ????16 | ????24 | ????31 | ????20 | ????32 | ||
| The polyisocyanate solution title | ????P-21 | ????P-22 | ????P-23 | ????P-24 | ????P-25 | ||
| Synthetic post analysis value | Isocyanate content (%) | ????8.7 | ????13.3 | ????14.8 | ????13.3 | ????6.5 | |
| Solids component (%) | ????50 ? | ????75 ? | ????80 ? | ????75 ? | ????40 ? | ||
Table 15
| Comparative example | ||||||||||||||||
| ??45 | ??46 | ??47 | ??48 | ??49 | ??50 | ??51 | ??52 | ??53 | ??54 | ??55 | ??56 | ??57 | ??58 | ??59 | ||
| Organic multiple isocyanate (g) | コ ロ ネ one ト T-100 | ??900 | ??- | ??- | ??- | ??- | ??- | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? |
| コ ロ ネ one ト T-80 | ??- ? | ??890 ? | ??796 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??900 ? | ??930 ? | ??908 ? | ??920 ? | ??- ? | ??- ? | |
| コ ロ ネ one ト T-65 | ??- ? | ??- ? | ??- ? | ??900 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??， ? | ??- ? | ??- ? | ??- ? | ??- ? | ??900 ? | |
| ??HD1 | ??- | ??- | ??- | ??- | ??900 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| ミ リ オ ネ one ト MTL | ??- | ??- | ??- | ??- | ??- | ??900 | ??930 | ??908 | ??920 | ??- | ??- | ??- | ??- | ??900 | ??- | |
| Polyvalent alcohol (g) | ??TMP | ??40 | ??25 | ??204 | ??40 | ??25 | ??30 | ??- | ??31 | ??45 | ??30 | ??- | ??31 | ??45 | ??30 | ??30 |
| ??Gly | ??5 | ??65 | ??- | ??4 | ??8 | ??32 | ??40 | ??5 | ??3 | ??32 | ??40 | ??5 | ??3 | ??15 | ??15 | |
| ??EG | ??5 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| ??1，3-BD | ??40 | ??5 | ??- | ??10 | ??20 | ??18 | ??15 | ??10 | ??10 | ??18 | ??15 | ??10 | ??10 | ??18 | ??18 | |
| ??PRD ? | ??- ? | ??- ? | ??- ? | ??- ? | ??20 ? | ??20 ? | ??15 ? | ??- ? | ??10 ? | ??20 ? | ??15 ? | ??- ? | ??10 ? | ??20 ? | ??20 ? | |
| ??PND | ??- | ??10 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| ??DPG | ??10 | ??5 | ??- | ??- | ??27 | ??- | ??， | ??- | ??- | ??- | ??- | ??- | ??- | ??17 | ??17 | |
| ??PP-400 | ??- | ??- | ??- | ??46 | ??- | ??- | ??- | ??46 | ??12 | ??- | ??- | ??46 | ??12 | ??- | ??- | |
| Stabilization agent (g) | ??AC ? | ??- ? | ??- ? | ??- ? | ??0.1 ? | ??- ? | ??0.1 ? | ??0.1 ? | ??0.1 ? | ??0.1 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??0.1 ? | ??- ? |
| Organic solvent (g) | Toluene | ??500 | ??- | ??- | ??- | ??500 | ??- | ??- | ??- | ??- | ??100 | ??100 | ??100 | ??100 | ??- | ??100 |
| Vinyl acetic monomer | ??- | ??333 | ??1000 | ??333 | ??- | ??333 | ??333 | ??コ33 | ??333 | ??233 | ??233 | ??233 | ??233 | ??333 | ??- | |
| Methyl ethyl ketone | ??500 | ??- | ??1333 | ??- | ??500 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??233 | |
| ??????????f2 | ??53 | ??14 | ??0 | ??31 | ??63 | ??35 | ??36 | ??35 | ??33 | ??35 | ??36 | ??35 | ??33 | ??50 | ??50 | |
| ??????????f3 | ??47 | ??86 | ??100 | ??69 | ??37 | ??65 | ??64 | ??65 | ??67 | ??65 | ??64 | ??65 | ??67 | ??50 | ??50 | |
| The G value | ??7 | ??68 | ??0 | ??9 | ??12 | ??40 | ??64 | ??12 | ??6 | ??40 | ??64 | ??12 | ??6 | ??21 | ??21 | |
| The polyisocyanate solution title | ??P-26 ? | ??P-27 ? | ??P-28 ? | ??P-29 ? | ??P-30 ? | ??P-31 ? | ??P-32 ? | ??P-33 ? | ??P-34 ? | ??P-35 ? | ??P-36 ? | ??P-37 ? | ??P-38 ? | ??P-39 ? | ??P-40 ? | |
| Synthetic post analysis value | Isocyanate content (%) | ??9.0 ? | ??11.7 ? | ??* ? | ??15.1 ? | ??9.1 ? | ??24.3 ? | ??27.3 ? | ??28.7 ? | ??28.1 ? | ??12.2 ? | ??13.9 ? | ??15.1 ? | ??14.5 ? | ??25.2 ? | ??13.3 ? |
| Solids component (%) | ??50 ? | ??75 ? | ??* ? | ??75 ? | ??50 ? | ??75 ? | ??75 ? | ??75 ? | ??75 ? | ??75 ? | ??75 ? | ??7S ? | ??7S ? | ??75 ? | ??75 ? | |
* can not measure because of bad order
PAC represents the phthalic acid dichloride in the above-mentioned table 14,15, and FBA represents fluorobenzoic acid, and AC represents acetic acid.F2, f3, G value, other trade(brand)name and be called for short as mentioned above.
In the polyisocyanate solution that the various embodiments described above and comparative example obtain, record the viscosity behind firm preparation back viscosity and 50 ℃, 30 days, be shown in table 16.
Viscosity is measured viscosity according to the Canon Off エ Application ス ケ viscometer of JIS K 2283-1980 regulation.
Known polyisocyanates usually is owing to have an isocyanate group endways, thus between the shelf lives because and the reaction high molecular of moisture etc., the solvability of solvent is reduced.So as an index of stability in storage, the solvent solubility behind evaluation of measuring above-mentioned each polyisocyanate solution preparation back solvent solubility and 50 ℃, 30 days is shown in table 16 in the lump.
Utilize following test method to carry out the evaluation of measuring of solvent solubility.
The solvent solubility test
Get polyisocyanate solution 5g, utilize drop-burette progressively to add toluene slightly, shake well is defined as terminal point when muddiness occurring, tries to achieve the ml of required solvent this moment.Utilize following formula to try to achieve solvent solubility (doubly) then.Its value is big more, and solvent solubility is good more.
Ml number/the sample size (5g) of solvent solubility (doubly)=required solvent.
Table 16
| The solution title | After synthetic | 50 ℃, after 30 days | |||
| Viscosity (25 ℃) (mm 2/s) | Solvent solubility (doubly) | Viscosity (25 ℃) (mm 2/s) | Solvent solubility (doubly) | ||
| Embodiment 16 | ?P-21 | ????7 | ????38 | ????9 | ????36 |
| Embodiment 17 | ?P-22 | ????1290 | ????43 | ????1360 | ????40 |
| Embodiment 18 | ?P-23 | ????3200 | ????35 | ????3350 | ????34 |
| Embodiment 19 | ?P-24 | ????1280 | ????45 | ????1390 | ????41 |
| Embodiment 20 | ?P-25 | Below 5 | ????40 | ????8 | ????37 |
| Comparative example 45 | ?P-26 | ????10 | ????15 | ????90 | ????10 |
| Comparative example 46 | ?P-27 | ????1500 | ????9 | ????3720 | ????4 |
| Comparative example 47 | ?P-28 | ????* | ????* | ????* | ????* |
| Comparative example 48 | ?P-29 | ????780 | ????13 | ????1460 | ????8 |
| Comparative example 49 | ?P-30 | ????5 | ????23 | ????50 | ????15 |
| Comparative example 50 | ?P-31 | ????2100 | ????6 | ????4500 | ????3 |
| Comparative example 51 | ?P-32 | ????1300 | ????8 | ????3100 | ????3 |
| Comparative example 52 | ?P-33 | ????1000 | ????9 | ????3000 | ????3 |
| Comparative example 53 | ?P-34 | ????1100 | ????8 | ????3000 | ????3 |
| Comparative example 54 | ?P-35 | ????1450 | ????11 | ????3300 | ????5 |
| Comparative example 55 | ?P-36 | ????1020 | ????10 | ????2800 | ????6 |
| Comparative example 56 | ?P-37 | ????790 | ????13 | ????1540 | ????8 |
| Comparative example 57 | ?P-38 | ????900 | ????11 | ????2100 | ????7 |
| Comparative example 58 | ?P-39 | ????1700 | ????6 | ????3300 | ????3 |
| Comparative example 59 | ?P-40 | ????1100 | ????11 | ????2000 | ????6 |
* can not measure because of outward appearance is bad.
Shown in table 16, contain isocyanate group terminal amino group manthanoate prepolymer (A), organic solvent (B), etheride (C) even the polyisocyanate solution of embodiment 16～20 behind the high temperature storage, almost do not have viscosity to reduce and the reduction of solvent solubility yet.To this, do not use the polyisocyanate solution of the comparative example 45～59 of etheride (C), viscosity rises significantly, and solvent solubility also reduces significantly.
And, utilize the compatibility test to other resin of above-mentioned each polyisocyanate solution of following method test.
Compatibility test
Mix above-mentioned each polyisocyanate solution at 1: 1 with various resins shown in table 17 and the table 18 and mass ratio, the mixed solution that obtains is coated on the sheet glass, 120 ℃ made solvent evaporates fully through 1 hour afterwards, according to following judgement criteria, and the appearance of film below estimating.The result is shown in the table 17,18 in the lump.
Zero: transparent, △: have a little mist, *: opaque.
Table 17
| Consistency with other resins | Embodiment | |||||
| ??16 | ??17 | ??18 | ??19 | ??20 | ||
| After synthetic | ??ニツポラン1100 | ??○ | ??○ | ??○ | ??○ | ??○ |
| ??アクリデイツク ??A-801 | ??○ ? | ??○ ? | ??○ ? | ??○ ? | ??○ ? | |
| Nitro-cotton | ??○ ? | ??○ ? | ??○ ? | ??○ ? | ??○ ? | |
| Vinylchlorid-vinyl-acetic ester | ??○ | ??○ | ??○ | ??○ | ??○ | |
| ??CAB | ??○ | ??○ | ??○ | ??○ | ??○ | |
| 50 ℃, after 30 days | ??ニツポラン1100 | ??○ | ??○ | ??○ | ??○ | ??○ |
| ??アクリデイツク ??A-801 | ??○ ? | ??○ ? | ??○ ? | ??○ ? | ??○ ? | |
| Nitro-cotton | ??○ | ??○ | ??○ | ??○ | ??○ | |
| The ammonia ethane-acetic acid ethyenyl ester | ??○ | ??○ | ??○ | ??○ | ??○ | |
| ??CAB | ??○ | ??○ | ??○ | ??○ | ??○ | |
ニ Star Port ラ Application 1100: Japanese polyurethane industry system polyester polyol
ア Network リ デ イ Star Network A-801: big Japanese ink chemical industry (strain) system acrylate copolymer
Nitro-cotton: Asahi Chemical Industry's industry (strain) system nitro-cotton セ Le ノ バ BTH1/2
Ammonia ethane-acetic acid ethyenyl ester: ponding chemical industry preparing chloroethylene-vinyl acetate copolymer.
CAB:Eastman chemistry (strain) system cellulose acetate butyl ester
Table 18
| Consistency with other resins | Comparative example | |||||||||||||||
| ??45 | ??46 | ????47 | ??48 | ??49 | ??50 | ??51 | ??52 | ??53 | ??54 | ??55 | ??56 | ??57 | ??58 | ??59 | ||
| After synthetic | ??ニツポラン ??1100 | ??○ ? | ??△ ? | ????* ? | ??○ ? | ??○ ? | ??△ ? | ??○ ? | ??○ ? | ??○ ? | ??△ ? | ??△ ? | ??○ ? | ??○ ? | ??△ ? | ??△ ? |
| ??アクリデイ ? ??ツクA-801 | ??× ? | ??× ? | ????* ? | ??○ ? | ??○ ? | ??× ? | ??○ ? | ??○ ? | ??○ ? | ??△ ? | ??× ? | ??○ ? | ??○ ? | ??× ? | ??△ ? | |
| Nitro-cotton | ??△ | ??△ | ????* | ??△ | ??△ | ??× | ??△ | ??△ | ??△ | ??△ | ??△ | ??△ | ??△ | ??× | ??△ | |
| Vinylchlorid-vinyl-acetic ester | ??△ ? | ??△ ? | ????* ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | |
| ??CAB | ??△ | ??× | ????* | ??× | ??△ | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | |
| 50 ℃, after 30 days | ??ニツポラン ? ??1100 | ??△ ? | ??△ ? | ????* ? | ??○ ? | ??○ ? | ??△ ? | ??○ ? | ??○ ? | ??○ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? |
| ??アクリデイ ??ツク ??A-801 | ??× ? | ??× ? | ????* ? | ??○ ? | ??△ ? | ??× ? | ??○ ? | ??○ ? | ??○ ? | ??× ? | ??× ? | ??△ ? | ??△ ? | ??× ? | ??× ? | |
| Nitro-cotton | ??× | ??× | ????* | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | |
| Vinylchlorid-vinyl-acetic ester | ??△ ? | ??△ ? | ????* ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | ??△ ? | |
| ??CAB | ??× | ??× | ????* | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | ??× | |
* because of bad order, can not measure
ニ Star Port ラ Application 1100: Japanese polyurethane industry system polyester polyol
ア Network リ デ イ Star Network A-801: big Japanese ink chemical industry (strain) system acrylate copolymer
Nitro-cotton: Asahi Chemical Industry's industry (strain) system nitro-cotton セ Le ノ バ BTH1/2
Vinylchlorid-vinyl-acetic ester: ponding chemical industry preparing chloroethylene-vinyl acetate copolymer.
CAB:Eastman chemistry (strain) system cellulose acetate butyl ester
As shown in table 17,18, the relatively routine polyisocyanate solution of polyisocyanate solution of embodiment 16～20 preparations has the good consistency to other resin.
[5] caking agent estimates 2
Embodiment 21～25, comparative example 60～74
Polyisocyanate solution P-21～40 that obtain with the foregoing description 16～20 and comparative example 45～59 are as stiffening agent, caking agent as host, utilizes following method to estimate the caking agent of 2 liquid types with the ニ Star Port ラ Application 3016 (Japanese polyurethane industry (strain) system, ethyl acetate solution, hydroxyl amount=0.04mmol/g, solids component=22%) of polyurethane resin solution.
Hydroxyl and the isocyanate group in the stiffening agent that the proportioning of host and stiffening agent is made in the host are normal ratio.
Adhesive test
Urethane RIM (reaction injection molding(RIM) is molded) molding, FRP, ABS, steel plate (JISG3141 (3141-SB), model: PF-1077, Japanese testing instrument industry system, the bonding steel plate of following abbreviation with length 100mm, wide 25mm, thickness 1mm.) use the trieline degreasing, the adhesive applicating that cooperates above-mentioned host/stiffening agent on it and form is become dry film thickness 40～50 μ m, surface covered 25mm * 25mm.
50 ℃ of down dry 5 minutes of preparations, the solvent in the evaporation caking agent does not enter bubble, and 2 of above-mentioned each plates of same kind is overlapping then, compresses with 2.5Mpa, and it was placed 3 days in 20 ℃, the atmosphere of 65%RH, obtains bonding sample.
Thereafter, at draw speed=100mm/min, measure under the condition of atmosphere=23 ℃, 50%RH and record bonding shearing strength.The results are shown in table 19,20.
Table 19
| Adhesive test | Embodiment | ||||||
| ?21 | ?22 | ?23 | ?24 | ?25 | |||
| The polyisocyanate solution title | ?P-21 | ?P-22 | ?P-23 | ?P-24 | ?P-25 | ||
| After synthetic | By convered structure | ??RIM/RIM | ?24/A | ?21/A | ?21/A | ?24/A | ?23/A |
| ??FRP/FRP | ?18/A | ?19/A | ?17/A | ?18/A | ?16/A | ||
| ??ABS/ABS | ?21/A | ?21/A | ?19/A | ?21/A | ?19/A | ||
| Bonded steel/bonded steel | ?20/A ? | ?24/A ? | ?22/A ? | ?25/A ? | ?23/A ? | ||
| 50 ℃, after 30 days | By convered structure | ??RIM/RIM | ?22/A | ?21/A | ?20/A | ?23/A | ?22/A |
| ??FRP/FRP | ?17/A | ?18/A | ?16/A | ?17/A | ?15/A | ||
| ??ABS/ABS | ?20/A | ?20/A | ?18/A | ?20/A | ?17/A | ||
| Bonded steel/bonded steel | ?19/A ? | ?23/A ? | ?21/A ? | ?23/A ? | ?21/A ? | ||
Method for expressing: bonding strength (MPa)/collapse state
Collapse state A: aggegation destroys
Table 20
| Then property test | Comparative example | ||||||||||||||||
| 60 | 61 | ????62 | 63 | ?64 | 65 | 65 | 67 | 68 | 69 | 70 | 71 | 72 | 73 | 74 | |||
| The polyisocyanate solution title | P-26 | P-27 | ???P-2S | P-29 | ?P-30 | P-31 | P/32 | P-33 | P-34 | P-35 | P-36 | P-37 | P-3S | F-39 | P-40 | ||
| After synthetic | By convered structure | RIM/RIM | 24/A | 18/A | ????* | 22/A | ?9/A | 14/A | 14/A | 13/A | 14/A | 22/A | 21/A | 19/A | 21/A | 13/A | 21/A |
| FRP/FRP | 17/A | 18/A | ????* | 18/A | ?7/A | 10/A | 9/A | 8/A | 9/A | 19/A | 18/A | 17/A | 18/A | 10/A | 19/A | ||
| ABS/ABS | 21/A | 20/A | ????* | 20/A | ?6/A | 10/A | 11/A | 11/A | 11/A | 22/A | 21/A | 19/A | 21/A | 10/A | 21/A | ||
| Bonded steel/bonded steel | 20/A ? | 22/A ? | ????* ? | 21/A ? | ?10/A ? | 16/A ? | 15/A ? | 16/A ? | 16/A ? | 21/A ? | 22/A ? | 18/A ? | 21/A ? | 16/A ? | 21/A ? | ||
| 50 ℃, after 30 days | By convered structure | RIM/RIM | 13/A | 9/A | ????* | 11/A | ?5/A | 9/A | 10/A | 10/A | 11/A | 12/A | 9/A | 10/A | 11/A | 9/A | 11/A |
| FRP/FRP | 10/A | 11/A | ????* | 8/A | ?3/A | 6/A | 5/A | 6/A | 5/A | 11/A | 10/A | 10/A | 10/A | 6/A | 10/A | ||
| ABS/ABS | 10/A | 12/A | ????* | 9/A | ?3/A | 6/A | 7/A | 8/A | 8/A | 11/A | 13/A | 10/A | 11/A | 6/A | 11/A | ||
| Bonded steel/bonded steel | 15/A ? | 13/A ? | ????* ? | 12/A ? | ?5/A ? | 11/A ? | 11/A ? | 12/A ? | 12/A ? | 15/A ? | 12/A ? | 13/A ? | 12/A ? | 10/A ? | 14/A ? | ||
* because of bad order, can not measure
Method for expressing: bonding strength (MPa)/collapse state
Collapse state A: aggegation destroys
As table 19, shown in 20, the caking agent that the polyisocyanate solution that embodiment 16～20 is obtained obtains than comparative example 60～74 as the caking agent of the embodiment 21～25 of stiffening agent has the remarkable high bonding strength of various materials.
[6] coating assessment 2
[embodiment 26～30, comparative example 35～38]
Polyisocyanate solution as stiffening agent uses the foregoing description 16～20 and comparative example 45,46,48～49 to obtain fits in as table 21, shown in 22, cooperates mix polyisocyanate solution and other each coating raw materials, fits in coating.
The applying coating that cooperates like this on the bonding steel plate by the trieline degreasing, was placed for 1 week under 20 ℃, the environment of 65%RH, form filming of dry film thickness=40～50 μ m.And each rerum natura of filming that forms is measured, is estimated according to the method for JIS K5400.The results are shown in table 23, in 24.
Table 21, the material that each trade(brand)name is represented in 22 in detail as mentioned above.
Table 21
| Be coated with film test | Embodiment | |||||
| ????26 | ????27 | ????28 | ????29 | ????30 | ||
| Polyisocyanate solution (g) | ????P-21 ? ????180 | ????P-22 ? ????119 | ????P-23 ? ????202 | ????P-24 ? ????220 | ????P-25 ? ????372 | |
| Host (g) | ?ヒロイド ?3088 | ????420 | ????422 | ????- | ????- | ????- |
| ?ニツポラン800 ? | ????- ? | ????- ? | ????138 ? | ????135 ? | ????- ? | |
| ?ニツポラン ?1100 | ????- ? | ????- ? | ????- ? | ????- ? | ????151 ? | |
| Diluting solvent (g) | Toluene | ????100 | ????100 | ????200 | ????200 | ????- |
| Vinyl acetic monomer | ????100 | ????- | ????260 | ????- | ????100 | |
| N-BUTYL ACETATE | ????- | ????159 | ????- | ????245 | ????177 | |
| Pigment (g) | Titanium oxide | ????200 ? | ????200 ? | ????200 ? | ????200 ? | ????200 ? |
Table 22
| Be coated with film test | Comparative example | ||||||||||||||
| ??75 | ??76 | ??77 | ??78 | ??79 | ??80 | ??81 | ??82 | ??83 | ??84 | ??85 | ??86 | ??87 | ??88 | ||
| Polyisocyanate solution (g) | ??P-26 ??176 | ??P-27 ??233 | ??P-29 ??177 | ??P-30 ??175 | ??P-31 ??132 | ??P-32 ??122 | ??P-33 ??118 | ??P-34 ??120 | ??P-35 ??229 | ??P-36 ??216 | ??P-37 ??208 | ??P-38 ??212 | ??P-39 ??129 | ??P-40 ??220 | |
| Host (9) | ??ヒロ ??イド ??3088 | ??424 ? | ??- ? | ??- ? | ??425 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? | ??- ? |
| ??ニツポ ??ラン ? ??800 | ??- | ??125 | ??- | ??- | ??- | ??- | ??- | ??- | ??128 | ??138 | ??144 | ??141 | ??- | ??135 | |
| ??ニツポ ??ラン ??1100 | ??- ? | ??- ? | ??167 ? | ??- ? | ??201 ? | ??209 ? | ??212 ? | ??210 ? | ??- ? | ??- ? | ??- ? | ??- ? | ??203 ? | ??- ? | |
| Diluting solvent (g) | Toluene | ??100 | ??200 | ??- | ??100 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 | ??200 |
| Vinyl acetic monomer | ??100 | ??- | ??200 | ??- | ??267 | ??269 | ??270 | ??270 | ??243 | ??246 | ??248 | ??247 | ??268 | ??245 | |
| N-BUTYL ACETATE | ??- | ??242 | ??256 | ??100 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | |
| Pigment (g) | Titanium oxide | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? | ??200 ? |
Table 23
| Be coated with film test | Embodiment | |||||||
| ????26 | ????27 | ????28 | ????29 | ????30 | ||||
| After synthetic | Gloss | ????94 | ????93 | ????91 | ????89 | ????93 | ||
| Drying property | Touch dry (branch) | ????16 | ????18 | ????50 | ????56 | ????54 | ||
| Dry through (branch) | ????38 | ????43 | ????110 | ????125 | ????120 | |||
| The impact of デ ユ Port Application (1/2 ", 500g) (cm) | ????90 | ????100 | ????90 | ????90 | ????100 | |||
| Bendability (2mm φ) | Qualified | Qualified | Qualified | Qualified | Qualified | |||
| Sven-Gan Eriksson value (mm) | ????8 | ????9 | ????7 | ????10 | ????7 | |||
| Pencil hardness | ????H | ????H | ????H | ????H | ????H | |||
| Stopping property (point) | ????10 | ????10 | ????10 | ????10 | ????10 | |||
| 50 ℃, after 30 days | Gloss | ????92 | ????91 | ????90 | ????89 | ????91 | ||
| Drying property | Touch dry (branch) | ????14 | ????17 | ????48 | ????53 | ????50 | ||
| Dry through (branch) | ????37 | ????41 | ????107 | ????118 | ????111 | |||
| The impact of デ ユ Port Application (1/2 ", 500g) (cm) | ????80 | ????90 | ????90 | ????80 | ????90 | |||
| Bendability (2mm φ) | Qualified | Qualified | Qualified | Qualified | Qualified | |||
| Sven-Gan Eriksson value (mm) | ????8 ? | ????8 ? | ????6 ? | ????9 ? | ????7 ? | |||
| Pencil hardness | ????H | ????H | ????H | ????H | ????H | |||
| Stopping property (point) | ????10 | ????10 | ????10 | ????10 | ????10 | |||
Table 24
| Be coated with film test | Comparative example | |||||||||||||||
| ??75 | ??76 | ??77 | ??78 | ??79 | ??80 | ??81 | ??82 | ??83 | ??84 | ??85 | ??86 | ??87 | ??88 | |||
| After synthetic | Gloss | ??92 | ??91 | ??91 | ??90 | ??76 | ??77 | ??78 | ??77 | ??92 | ??91 | ??90 | ??91 | ??76 | ??92 | |
| Drying property | Touch dry (branch) | ??65 ? | ??45 ? | ??70 ? | ??200 ? | ??180 ? | ??160 ? | ??130 ? | ??170 ? | ??63 ? | ??55 ? | ??58 ? | ??57 ? | ??170 ? | ??66 ? | |
| Dry through (branch) | ??140 ? | ??100 ? | ??150 ? | ??≥500 ? | ??380 ? | ??350 ? | ??290 ? | ??360 ? | ??130 ? | ??120 ? | ??140 ? | ??110 ? | ??370 ? | ??140 ? | ||
| The impact of デ ユ Port Application (1/2 ", 500g) (cm) | ??100 | ??90 | ??100 | ??≥150 | ??≥150 | ??≥150 | ??≥150 | ??≥150 | ??100 | ??90 | ??100 | ??90 | ?≥150 | ??100 | ||
| Bendability (2mm φ) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | ||
| Sven-Gan Eriksson value (mm) | ??8 | ??9 | ??10 | ??≥12 | ??≥12 | ??≥12 | ??≥12 | ??≥12 | ??8 | ??9 | ??8 | ??9 | ??≥12 | ??8 | ||
| Pencil hardness | ??H | ??H | ??H | ??B | ??B | ??B | ??B | ??B | ??H | ??H | ??H | ??H | ??B | ??H | ||
| Stopping property (point) | ??8 | ??9 | ??8 | ??10 | ??9 | ??9 | ??9 | ??9 | ??8 | ??9 | ??8 | ??8 | ??8 | ??8 | ||
| 50 ℃, after 30 days | Gloss | ??66 | ??51 | ??60 | ??65 | ??53 | ??52 | ??47 | ??51 | ??66 | ??51 | ??66 | ??51 | ??51 | ??63 | |
| Drying property | Touch dry (branch) | ??38 ? | ??28 ? | ??40 ? | ??145 ? | ??140 ? | ??110 ? | ??90 ? | ??110 ? | ??33 ? | ??31 ? | ??33 ? | ??28 ? | ??130 ? | ??31 ? | |
| Dry through (branch) | ??75 ? | ??56 ? | ??77 ? | ??≥500 ? | ??280 ? | ??240 ? | ??150 ? | ??240 ? | ??75 ? | ??56 ? | ??72 ? | ??56 ? | ??270 ? | ??73 ? | ||
| The impact of デ ユ Port Application (1/2 ", 500g) (cm) | ? ??60 ? | ? ??50 ? | ? ??70 ? | ? ??≥150 ? | ? ??110 ? | ? ??130 ? | ? ??120 ? | ? ??130 ? | ? ??δ0 ? | ? ??50 ? | ? ??60 ? | ? ??50 ? | ? ??110 ? | ? ??60 ? | ||
| Bendability (2mm φ) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Close network | Qualified | Qualified | Qualified | ||
| Sven-Gan Eriksson value (mm) | ??3 | ??4 | ??8 | ??≥12 | ??≥12 | ??≥12 | ??≥12 | ??≥12 | ??3 | ??3 | ??3 | ??3 | ??≥12 | ??3 | ||
| Pencil hardness | ??H | ??H | ??H | ??B | ??B | ??B | ??B | ??B | ??H | ??H | ??H | ??H | ??B | ??H | ||
| Stopping property (point) | ??3 | ??4 | ??4 | ??7 | ??6 | ??5 | ??4 | ??5 | ??3 | ??3 | ??3 | ??3 | ??5 | ??3 | ||
As table 23, shown in 24, the polyisocyanate solution that embodiment 16～20 obtains is compared with the coating of comparative example 75～88 as the coating among the embodiment 26～30 of stiffening agent, has each good film performance, has each characteristic such as good stopping property, hardness and drying property especially.In addition, at 50 ℃, do not see after 30 days that tangible performance reduces yet.
The present invention can obtain having the polyisocyanate solution of consistency, stability in storage of good hardness, drying property, solvent solubility, other resin etc., by using the polyisocyanate solution of these characteristic goods, can obtain the caking agent and the coating of superperformance.
Claims (5)
1. polyisocyanate solution, contain isocyanate group terminal amino group manthanoate prepolymer (A) and organic solvent (B), wherein isocyanate group terminal amino group manthanoate prepolymer (A) is by making organic multiple isocyanate (A1) and by 20～40 moles of % of the glycol that contains alcoholic hydroxyl (A2-1) and contain polyvalent alcohol (A2) reaction that 80～60 moles of % of triol (A2-2) of alcoholic hydroxyl form and obtain, it is characterized in that, the described triol of a part (A2-2) is a glycerol, and the described polyvalent alcohol (A2) of 15～35 moles of % is described glycerol.
2. polyisocyanate solution as claimed in claim 1 is characterized in that, described organic multiple isocyanate (A1) is a tolylene diisocyanate.
3. polyisocyanate solution as claimed in claim 1 or 2 is characterized in that, contains etheride (C).
4. caking agent is characterized in that, uses as any one described polyisocyanate solution in the claim 1～3.
5. coating is characterized in that, uses as any one described polyisocyanate solution in the claim 1～3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002351216 | 2002-12-03 | ||
| JP351216/2002 | 2002-12-03 | ||
| JP061172/2003 | 2003-03-07 | ||
| JP2003061172A JP4110397B2 (en) | 2002-12-03 | 2003-03-07 | Polyisocyanate solution and adhesive and paint using the same |
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| Publication Number | Publication Date |
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| CN1504490A true CN1504490A (en) | 2004-06-16 |
| CN100406488C CN100406488C (en) | 2008-07-30 |
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| BR9812576A (en) * | 1997-10-01 | 2000-10-03 | Dow Chemical Co | Liquid polymers prepared by modeling (tlp's) and reactive extrusion of these |
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2003
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- 2003-12-03 CN CNB2003101197521A patent/CN100406488C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100406488C (en) | 2008-07-30 |
| JP4110397B2 (en) | 2008-07-02 |
| JP2004231931A (en) | 2004-08-19 |
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